Available online at www.sciencedirect.

com

ScienceDirect
Procedia Environmental Sciences 31 (2016) 303 – 308

The Tenth International Conference on Waste Management and Technology (ICWMT)

Characterization and mass balance of PCDD/Fs during the co-

combustion of sewage sludge in a grate-type municipal solid waste
incineration
Lehuan Yua, Jing Zhenga, Xiaohua Yuanb, Hongjun Songc, Jia Pengb, Mingzhong Rena,*
a
South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655, P. R. China
b
Foshan Nanhai Green Renewable Energy Co., Ltd., Foshan 528225, P. R. China
c
Scientific Research Academy of Guangxi Environmental Protection, Nanning 530022, P. R. China

Abstract

The emission and distribution characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were
investigated during the co-combustion of sewage sludge (SS) with municipal solid waste (MSW) in a grate-type furnace, South
China. On the output side, the stack gas, slag and fly ash with the dioxin levels of 10.75 pg I-TEQ/Nm3, 4.98 pg I-TEQ/g and 294.9
pg I-TEQ/g, respectively, showed similarities in congener profiles. However, the input side presented a significantly different
congener profiles compared to that in the output side, which may attribute to the de novo synthesis. The predominant PCDD/Fs
contribution (>90%) in fly ash suggested it as the major sink of dioxins in the output side. A positive mass balance of PCDD/Fs
with the value of 12.09 μg I-TEQ/t-MF was demonstrated.

©
© 2016
2015Published by Elsevier
The Authors. B.V This
Published is an openB.V.
by Elsevier access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Tsinghua University/ Basel Convention Regional Centre for Asia and the Pacific.
Peer-review under responsibility of Tsinghua University/ Basel Convention Regional Centre for Asia and the Pacific
Keywords: polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs); co-combustion; sewage sludge; municipal solid waste; mass
balance

* Corresponding author. Tel.: +86-020-29119881; fax: +86-020-29119537.

E-mail address: renmingzhong@scies.org

1878-0296 © 2016 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Tsinghua University/ Basel Convention Regional Centre for Asia and the Pacific
doi:10.1016/j.proenv.2016.02.040
304 Lehuan Yu et al. / Procedia Environmental Sciences 31 (2016) 303 – 308

1. Introduction

The accelerated economic development and urbanization process have brought a considerable volume of sewage
sludges (SS) which comprise high levels of water, organic matter, and pathogenic agent contents. The production of
SS in China has dramatically increased at an annual rate of 4% in recent years1. Due to the shortcomings on fertilizer
recycling, landfilling, and sea dumping, incineration has been considered as an effective method for SS disposal due
to its advantages on stabilization, volume reduction and resource recovery2. Many countries strongly support the co-
incineration of SS as supplementary fuel in the operating incineration facilities, such as coal-fired power plants, cement
kilns, brick kilns and municipal solid waste incinerators (MSWIs).
Concentrated public concerns have been raised on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)
emission from incinerators, owing to their high toxicity and associated adverse health implications. Extensive studies
have been conducted to investigate the possible routes and mechanism leading to the formation of PCDD/Fs3-5, some
of which referred to mono-combustion and co-combustion of SS. Unfortunately, data on the emission and
characterization of PCDD/Fs are still limited. Furthermore, reports on co-incineration of semi-dried sludge are rare,
especially concerning co-incineration with MSW in a grate furnace incinerator. The continuous improvement of
incineration technology and the increasing amounts of MSWIs provide possibility for co-combustion of SS with MSW
in China6. It is of necessity to assess the real emissions of dioxin from all by-products derived from a modern MSWI,
for better understanding the environmental feasibility of co-incineration of SS with MSW in China.
Therefore in the present study, emissions and congener profiles of PCDD/Fs were demonstrated in the input and
output sides from a operating MSWI. Dioxin mass balance was as well calculated to determine how and where dioxins
emitted. To our best knowledge, this is the first comprehensive study conducted on a field grate furnace to assess the
real situation of PCDD/Fs characterization in China.

2. Materials and Methods

2.1. Basic Information on the MSWI.

The investigation was carried out on a continuously operating modern MSWI in South China. The capacity of the
MSWI is 1500 tons per day. The Mitsubishi-Martin grate-type furnace consists of three identical incinerating units,
with each the separate heat recovery system and air pollutant control devices (APCDs), including semi-dry scrubber
(SDS), activated carbon injection (ACI), and bag filter (BG). Ca(OH)2 emulsion are added to trap the acid gases in
the SDS. The co-incineration study was performed on one of the three units. The SS, obtained from a municipal waste
water treatment plant nearby, was dewatered to semi-dried SS with the moisture content of approximately 30 wt.%
before its mix with MSW. The operating conditions and parameters of the MSWI are depicted in Table 1.

Table 1. Operating conditions and Parameters of the MSWI.

Operating conditions Parameters
Daily capacity (t/d) 1500
Incineration units 3
Operation time (h/d) 24
Production of fly ashes per unit (t/d) 43
Production of slag per unit (t/d) 161
Flue gas per unit (Nm3/h) 109000
Fuel components SS : MSW = 1:10
 Lehuan Yu et al. / Procedia Environmental Sciences 31 (2016) 303 – 308 305

2.2. Sampling and Analytical Methodologies

Flue gas, slag, and fly ash samples in the output side, and mixed fuel (MF) made of 10 wt.% SS with MSW, were
collected thrice from the corresponding sampling sites. The mean value of PCDD/Fs was determined for the further
analysis. The PCDD/F flue gas were sampled isokinetically from the stack sampling point for 120-180 min, following
the American Standard Method EPA 23A and the relative Chinese standard measurement procedure. Before flue gas
sampling, 13C12-labeled sampling standards were spiked into an Amberlite XAD-2 resin. During the co-combustion
of 10% SS, bottom and fly ash samples were simultaneously collected every 2 hours until the samples weighed 2 kg.
The methods used for the PCDD/F analysis were adopted from EPA Method 1613B. The analytical procedures were
reported previously7. 13C12-labeled PCDD/Fs injection internal standards were added to the corresponding fractions
for calculation of the recovery rate, prior to the instrument analysis using a high-resolution gas chromatograph coupled
with a high-resolution mass spectrometer (HRGC/HRMS).
The analytical recoveries were 68.4%-129.8%. Laboratory method blanks were run for each batch of samples. The
international toxic equivalency quantity (I-TEQ) was calculated using the international toxicity equivalency factor (I-
TEF).

3. Results and Discussion

3.1. PCDD/Fs contents in the input and output samples from the MSWI.

Table 2 listed the PCDD/F concentrations measured on the output side, i.e. stack flue gas, fly ash and slag, of the
MSWI, in terms of total values and I-TEQ, respectively. The total PCDD/Fs from the stack gas, with the mean level
of 0.0108 ng I-TEQ/Nm3, was significantly lower than the newly emission standard limit of 0.1 ng I-TEQ/Nm3
established by the Chinese Ministry of Environmental Protection in 2014 (GB 18485—2014). It was as well
comparable to the reported PCDD/Fs emission from a MSWI in East China8, suggesting the feasibility of co-
combustion with SS in MSWI. The fly ash samples presented the mean dioxin levels of 0.294 ng I-TEQ/g after co-
incineration, which met the Japanese environmental quality standards for soil (less than 1 ng I-TEQ/g). The mean
dioxin content from the slag with the value of 4.98 ng I-TEQ/kg, was much lower than that of the fly ash, and was
lower than that of MSW monocombustion on a similar facility9.
Dioxin content from the input side is also listed in Table 2. The average concentration was around 8.80 ng I-
TEQ/kg, lower than the mono-combustion report in China9. Minor chlorine content in the present SS compared to the
studied MSW may attribute to the result.

3.2. Distribution characteristics of PCDD/Fs from the input to the output.

The profiles of seventeen 2,3,7,8-substituted PCDD/F congeners in both input (mixed fuel) and output (stack gas,
fly ash, and slag) sides were characterized in terms of concentration and I-TEQ, respectively (Fig. 1). As illustrated
in Fig. 1, similarities in both concentration and TEQ profiles in the output side could be found. In concentration units,
it can be observed that the more chlorine atoms substituted, the higher contribution of the 2,3,7,8,-PCDD congeners,
but the pattern of the 2,3,7,8,-PCDF congeners presented irregular. In I-TEQ units, the PCDD/Fs profiles were
characterized by the predominance of 2,3,4,7,8-PeCDF accounting for around 40% of the total I-TEQ value, which
have been identified as the most representative emission profile of the dioxin during the incineration of municipal
solid waste and sewage sludge10. However, remarkable differences could be found in the profiles from the input side
compared to those of the output side. The PCDD levels were significantly higher than those of PCDFs and the MF
concentration profile was significantly dominated by a high content of OCDD (>80%) followed by 1,2,3,4,6,7,8-
HpCDD (~5%). Such characteristic, together with the ratios of PCDFs to PCDDs transferred from <<1 in the input
side to >1 in the output side (Table 2), indicated the de novo synthesis played the dominant role in the low-temperature
post-combustion zone.
306 Lehuan Yu et al. / Procedia Environmental Sciences 31 (2016) 303 – 308

Table 2 Mean concentrations of 2,3,7,8-substituted PCDD/Fs in flue gas, fly ash and slag samples.

Flue gas Fly ash Slag Mixed Fuel

PCDD/Fs I-TEF ng I- ng I-
3
ng/Nm ng/kg ng/kg ng I-TEQ/kg ng/kg ng I-TEQ/kg
TEQ/Nm3 TEQ/kg
2378-TCDF 0.100 0.001 0.00012 173.3 17.3 2.47 0.25 3.70 0.37
12378-PeCDF 0.050 0.003 0.00017 281.0 14.0 3.34 0.17 2.22 0.07
23478-PeCDF 0.500 0.007 0.00372 232.0 116.3 3.79 1.90 1.54 0.55
123478-HxCDF 0.100 0.007 0.00065 207.3 20.7 5.28 0.53 3.22 0.32
123678-HxCDF 0.100 0.009 0.00094 222.7 22.3 4.73 0.47 2.56 0.26
234678-HxCDF 0.100 0.015 0.00148 147.7 14.8 4.68 0.47 2.73 0.27
123789-HxCDF 0.100 0.001 0.00000 32.7 3.3 1.11 0.04 0.50 0.05
1234678-HpCDF 0.010 0.045 0.00045 397.7 4.0 22.50 0.23 10.72 0.11
1234789-HpCDF 0.010 0.013 0.00013 55.0 0.5 3.05 0.03 1.30 0.01
OCDF 0.001 0.088 0.00009 143.3 0.1 23.20 0.02 41.29 0.04
2378-TCDD 1.000 N.D. 0.00000 33.3 33.3 0.44 0.00 5.32 5.32
12378-PeCDD 0.500 0.001 0.00000 58.0 29.0 0.79 0.32 1.31 0.34
123478-HxCDD 0.100 0.003 0.00020 30.9 3.1 0.87 0.05 0.57 0.06
123678-HxCDD 0.100 0.013 0.00127 64.3 6.4 1.63 0.16 1.75 0.18
123789-HxCDD 0.100 0.005 0.00053 47.4 4.7 1.50 0.15 0.89 0.09
1234678-HpCDD 0.010 0.089 0.00089 412.0 4.1 14.23 0.14 29.45 0.30
OCDD 0.001 0.110 0.00011 867.0 0.9 55.97 0.06 479.11 0.48
Total PCDD/Fs 0.410 0.0108 3405.6 294.9 148.44 4.98 588.18 8.80
Total PCDFs 0.189 1892.7 73.96 69.78 2.05
Total PCDDs 0.221 1512.9 74.48 518.40 6.75
PCDFs : PCDDs 0.847 1.623 1.007 0.135

3.3. Dioxin mass balance from the input to the output.

To evaluate the real situation of dioxin emission in a grate-type MSWI that cofired 10% SS with MSW, mass
balance in terms of emission factors from the input to the output was calculated. The dioxin input via the MF was
compared with the sum of the dioxin output in flue gas, fly ash, and slag. The basic information listed in Table 1,
including the amount of MF treated, production of slag and fly ash as well as flow rates of flue gas under steady
running condition of the MSWI during the sampling period, were adopted for the evaluation. The mean PCDD/F
emission factors of the whole MSWI system were 1.24 μg I-TEQ/t-MF for slag, 19.6 μg I-TEQ/t-MF for fly ash, and
0.044 μg I-TEQ/t-MF for stack gas, respectively. Total emission factors of 20.89 μg I-TEQ/t-MF were demonstrated,
slightly lower than the results reported on an MSW monoincineration facility (22 μg I-TEQ/t-waste)9. However, as
shown in Table 3, the total emission factor of 8.80 μg I-TEQ/t-MF was evaluated on the input side, signifying a
positive dioxin mass balance of 12.09 μg I-TEQ/t-MF. The positive balance of PCDD/Fs was previously found in
other MSWI, which inferred a regeneration of dioxin in the post-combustion zone11.

Table 3 PCDD/Fs mass balance during SS and MSW co-incineration.

Items Parameters
Input Mixed fuel (μg I-TEQ/t-MF) 8.80
 Lehuan Yu et al. / Procedia Environmental Sciences 31 (2016) 303 – 308 307

Output Total output (μg I-TEQ/t-MF) 20.89

Slag (μg I-TEQ/t-MF) 1.24
Slag (%) 6.0
Fly ash (μg I-TEQ/t-MF) 19.6
Fly ash (%) 93.8
Flue gas (μg I-TEQ/t-MF) 0.044
Flue gas (%) 0.2
Mass balance (μg I-TEQ/t-MF) 12.09
APCD efficiencies Dioxin concentration at the APCD inlet (ng/Nm3) 15.7
Dioxin concentration at the stack (ng/Nm3) 0.410
Dioxin removal efficiency (%) 97.4
3
Dioxin concentration at the APCD inlet (ng I-TEQ/Nm ) 1.87
Dioxin concentration at the stack (ng I-TEQ/Nm3) 0.011
Dioxin removal efficiency (%) 99.4

45
45
40 Flue gas Flue gas
(A1)
Fly ash 40 Fly ash
35 Slag Slag
35
30
30
Contribution / %

(B1)
25
25
20 20
15 15
10 10
5 5

0 0
90
60
80
Mixed Fuel (A2) Mixed Fuel (B2)
70 50
60
Contribution / %

40
50

40 30

30
20
20
10
10

0 0
DF DF DF DF DF DF DF DF DF DF DD DD DD DD DD DD DD DF DF DF DF DF DF DF DF DF DF DD DD DD DD DD DD DD
-TC eC eC xC xC xC xC pC pC OC8-TC-PeC-HxC-HxC-HxC-HpC OC -TC eC eC xC xC xC xC pC pC OC8-TC-PeC-HxC-HxC-HxC-HpC OC
78 8-P 8-P 8-H 8-H 8-H 9-H 8-H 9-H 7 8 8 8 9 8 78 8-P 8-P 8-H 8-H 8-H 9-H 8-H 9-H
23 237 347 347 367 467 378 467 478 23 237 347 367 378 467 23 237 347 347 367 467 378 467 478 7 8 8 8 9 8
23 237 347 367 378 467
1 2 12 12 23 12 23 23 1 12 12 12 23 1 2 12 12 23 12 23 23 1 12 12 12 23
1 1 1 1 1 1

Fig. 1. Congener profiles of PCDD/Fs in the output side (A1, B1) and the input side (A2, B2).
(A) Concentration distribution; (B) I-TEQ distribution.

Expressed by percentage distribution, stack gas emissions constituted a minor fraction to the total dioxin output of
around 0.2%, whereas the greatest contribution was attributed to fly ashes with 93.8% followed by slag with 6.0%
308 Lehuan Yu et al. / Procedia Environmental Sciences 31 (2016) 303 – 308

(Table 3). This dioxin distribution in the three matrix on the output side was in line with the previous study on a
modern MSWI, in which the contribution of stack gas, slag, and fly ashes to the total emission factors was 1.4%,
14.4%, and 84.2%, respectively 9. However, the less contribution of stack gas and slag while the significantly higher
proportion of fly ashes was found when comparing the present study with those of the Zhang’s one 9. This result may
be attributed to the greater dioxin removal efficiency in the present APCD (Table 3), indicating larger amount of
dioxins were transferred into fly ash in the SDS and BG process on the present MSWI system.

4. Conclusion

The detailed PCDD/PCDF distribution characteristics and mass balance of the different components constituting
the dioxin inputs and outputs were investigated during the co-combustion of 10% SS with MSW in a grate-type furnace.
The dioxin emission was 0.0108 ng I-TEQ/Nm3, which was far below the legal emission standard limit of China. The
output samples showed similarities in congener profiles, whereas the MSW from the input side showed a remarkably
different dioxin pattern. De novo synthesis may attribute to the transformation. A positive dioxin mass balance of
12.09 μg I-TEQ/t-MF was evaluated in the studied MSWI, suggesting the dioxin regeneration progress in the post-
combustion zone. The dominant contribution of fly ashes to the total emission factors (>90%) demonstrated the ash
as the major sink of dioxins. Accordingly, taking SDS + ACI + BG as APCD, dioxin emission could be effectively
controlled below 0.1 ng I-TEQ/Nm3 when co-firing SS with MSW.

Acknowledgements

This research was supported by the Science and Technology Project of Guangdong Province (Grant No.
2014B020216006).

References

1. Deng WY, Yan JH, Li XD, Wang F, Chi Y, Lu SY. Emission characteristics of dioxins, furans and polycyclic aromatic hydrocarbons during
fluidized-bed combustion of sewage sludge. J Environ Sci 2009; 21 (12): 1747−52.
2. Khiari B, Marias F, Zagrouba F, Vaxelaire J. Use of a transient model to simulate fluidized bed incineration of sewage sludge. J. Hazard.
Mater. 2006; 135: 200-9.
3. Tuppurainen K, Halonen I, Ruokojärvi P, Tarhanen J, Ruuskanen J. Formation of PCDDs and PCDFs in municipal waste incineration and its
inhibition mechanisms: A review. Chemosphere 1998; 36(7): 1493−511.
4. McKay G. Dioxin characterisation, formation and minimisation during municipal solid waste (MSW) incineration: review. Chem Eng
J 2002; 86(3): 343−68.
5. Stanmore BR. The formation of dioxins in combustion systems. Combust Flame 2004; 136(3): 398−427.
6. Cheng H, Hu Y. Curbing dioxin emissions from municipal solid waste incineration in China: re-thinking about management policies and
practices. Environ. Pollut. 2010; 158: 2809-14. 3
7. Zhang G, Hai J, Ren MZ, Zhang SK, Cheng J, Yang ZR. Emission, mass balance, and distribution characteristics of PCDD/Fs and heavy
metals during cocombustion of sewage sludge and coal in power plants. Environ. Sci. Technol. 2013; 47: 2123−30. 4
8. Chen ZL, Wen JM, Liu CY, Zhang HT, Yang SQ, Tang X, Chen Q. Validity study on co-incineration of municipal sewage sludge and
municipal solid waste. J Environ Eng-China 2014; 8(1): 324-8. 5
9. Zhang G, Hai J, Cheng J. Characterization and mass balance of dioxin from a large-scale municipal solid waste incinerator in China. Waste
Manage. 2012; 32 (6): 1156−62.6
10. Conesa JA, Font R, Fullana A, Martin-Gullon I, Aracil I, Galvez A, Molto J, Gomez-Rico MF. Comparison between emissions from the
pyrolysis and combustion of different wastes. J Anal Appl Pyrol 2009; 84: 95-102.7
11. Abad E, Adrados MA, Caixach J, Fabrellas B, Rivera J. Dioxin mass balance in a municipal waste incinerator. Chemosphere 2000; 40: 1143-
7.8